HK1069840B - Polycarbonate having a pronounced shear thinning behavior - Google Patents

Description

Polycarbonates with significant shear thinning behavior

Technical Field

The present invention relates to a novel branched melt polymerized polycarbonate having a pronounced non-Newtonian flow behaviour, to compositions containing such polycarbonate and to moulded objects produced therefrom. The invention also relates to a method for producing such polycarbonates.

Polycarbonates are produced industrially by the interfacial process or by transesterification in the melt (melt polymerization process). Melt polymerization processes are increasingly gaining in importance because they can be carried out without the use of phosgene or chlorinated solvents. As the method mainly used at present, the interfacial method, the polycarbonate produced is linear, and this polymer does not contain a polyfunctional structural unit. Linear polycarbonates of this type have only slight non-Newtonian flow behaviour owing to the lack of structural units which are capable of branching. To achieve branching in the interfacial process, branching agents must be added. Due to the branching caused by the multifunctional building blocks, the flowability of the polymer increases at low shear rates and decreases at high shear rates.

Polycarbonates produced by the melt polymerization process necessarily contain polyfunctional structural units. The inevitable formation of multifunctional branching structural units during polymerization is known, for example, from Angewandte Chemie 20, pp.633-660, 1956.

U.S. Pat. No. 5,5932683 describes a melt process by which a melt polycarbonate having three specific structural units is formed. The specific relationship between reaction time and reaction temperature is described as a parameter for the preparation of the polycarbonate. The polycarbonates described have a particularly easy flow behaviour at high shear rates. However, such flow behavior is often accompanied by poor flow at low shear rates.

It was therefore an object of the present invention to develop a melt polycarbonate which, in addition to good flowability at high shear rates, also has no flowability at low shear rates which is lower than that of an unbranched polycarbonate.

This object has been achieved by a melt process which does not correspond to the parameters mentioned in US 5932683, the melt polycarbonate produced comprising novel tetrafunctional structural units. However, this particular branched polycarbonate, while having improved flow behavior at high shear rates, also exhibits flow at low shear rates comparable to the unbranched polycarbonates prepared by the interfacial process. The polycarbonates according to the invention can therefore be employed particularly successfully in injection molding, and in addition they are comparable to unbranched polycarbonates in extrusion.

The polycarbonates according to the invention have the general formula (1)

Wherein the square brackets in the parentheses represent the repeating structural units of the polycarbonate,

m may be Ar or a polyfunctional compound A,

wherein

Ar may be a compound represented by the general formula (2)

Or, particularly preferably, a compound represented by the general formula (3)

Wherein

Z represents C₁～C₈Alkylidene or C₅～C₁₂Cycloalkylidene, S, SO₂Or a single bond, or a mixture of single bonds,

r represents a substituted or unsubstituted phenyl, methyl, propyl, ethyl, butyl, Cl or Br, and

n represents 0, 1 or 2,

wherein

Y is hydrogen or a compound of formula (4)

Wherein

R' may be H, C₁～C₂₀Alkyl radical, C₆H₅Or C (CH)₃)₂C₆H₅May be the same or different, and

n represents 0, 1, 2 or 3,

wherein the polyfunctional compound A is a compound of the formula

Wherein

X is Y or- (MOCOO) Y as in compounds B, C and D below,

wherein M and Y have the meanings specified above,

and may be present in the polycarbonate in an amount of 201 to 5000ppm, preferably 350 to 2000ppm, most preferably 300 to 1000 ppm.

Compound A is particularly preferably a compound of the formula

The polycarbonates according to the invention may additionally comprise compounds B, C and D.

The compound B may be a polyfunctional compound of the formula

And may be present in the polycarbonate in an amount of 1501 to 10,000ppm, preferably 1550 to 3000ppm, most preferably 1600 to 2000 ppm.

Compound B is particularly preferably a compound of the formula

The compound C may be a polyfunctional compound of the formula

And may be present in the polycarbonate in an amount of 351 to 5000ppm, preferably 400 to 2000ppm, most preferably 450 to 1000 ppm.

Compound C is particularly preferably a compound of the formula

In compounds a1, B, B1, C and C1, X is as defined for compound a.

Compound D may be a compound of the formula

And can be present in the polycarbonate in an amount of 751 to 5000ppm, preferably 800 to 2000ppm, most preferably 850 to 1500 ppm.

Compound D is particularly preferably a compound of the formula

The weight average molecular weight of the polycarbonate of the present invention is 5,000 to 80,000, preferably 10,000 to 60,000, and most preferably 15,000 to 40,000, as measured by gel permeation chromatography.

The polycarbonates according to the invention can also be defined by the shear thinning ratio y according to the formula,

y＞0.30+0.1312x^14.881，

where x is the relative viscosity of the polycarbonate.The shear-thinning ratio is used to quantitatively describe the flow behavior. Shear thinning ratio is defined as the ratio of the viscosity at low shear rate to the viscosity at high shear rate. According to the invention, the shear-thinning ratio is 50s^-1Viscosity at a shear rate of 5,000s^-1The ratio of the viscosities at shear rates, determined at 280 ℃.

Despite the high degree of branching and the associated pronounced non-Newtonian flow behaviour, the polycarbonates according to the invention have excellent colour and colour stability during injection moulding. It exhibits a much more slight yellowing than known melt polycarbonates.

The preparation of aromatic polycarbonates by the melt transesterification process is known and described, for example, in "Schnell", volume 9, International scientific Press, New York, London, Sydney 1964; see d.c. prevorsek, b.t.debona and y.kesten, union chemical company, research center for company, Moristown, new jersey 07960, "synthesis of poly (ester) carbonate copolymers", journal of polymer science, the chapter of polymer chemistry, volume 19, 75-90 (1980); see d.freitag, u.grigo, p.r.muller, n.nouvertne, bayer, "polycarbonate", by polymer science and engineering profession, volume 11, second edition, 1988, pp.648-718; and finally, see des.u.grigo, k.kircher and p.r.muller "polycarbonates", by Becker, Braun, handbook of plastics, volume 3/1, "polycarbonates, polyacetals, polyesters, cellulose esters", Carl Hanser press, munich, vienna, 1992, pp.117-299.

The polycarbonates according to the invention, which may also be polyester carbonates, are prepared by melt polymerization of suitable diphenols and/or carbonate oligomers having terminal OH groups or terminal carbonate groups in the presence of suitable catalysts. The polycarbonates may also be obtained by condensation of carbonate oligomers containing terminal hydroxyl groups or terminal carbonate groups with suitable diphenols and diaryl carbonates.

For the purposes of the present invention, a suitable diaryl carbonate is di-C₆～C₁₄Aryl esters, preferably benzeneDiesters of phenol or alkyl-substituted phenols, i.e., diphenyl carbonate, di (tolyl) carbonate and di-4-tert-butylphenyl carbonate. Diphenyl carbonate is most preferred.

Suitable carbonate oligomers are described by formula (1) above and have a molecular weight of 220 to 15,000.

Suitable di-C₆～C₁₄Aryl esters also include asymmetric diaryl esters that contain a mixture of aryl substituents. Most preferred are phenyl-cresyl carbonate and 4-tert-butylphenyl phenyl carbonate.

Suitable diaryl esters also include one or more di-C₆～C₁₄A mixture of aryl esters. The most preferred mixture is a mixture of diphenyl carbonate, di (tolyl) carbonate and di (4-tert-butylphenyl) carbonate.

1.00 to 1.30mol, particularly preferably 1.02 to 1.20mol, most preferably 1.05 to 1.15mol, of diaryl carbonate can be used per 1mol of diphenol.

For the purposes of the present invention, suitable dihydroxybenzene compounds are those corresponding to the general formula (5):

wherein

R is substituted or unsubstituted phenyl, methyl, propyl, ethyl, butyl, Cl or Br, and

n represents 0, 1 or 2.

The most preferred dihydroxybenzene compounds are 1, 3-dihydroxybenzene, 1, 4-dihydroxybenzene and 1, 2-dihydroxybenzene.

Suitable diphenols for the purposes of the present invention are those corresponding to the general formula (6):

wherein

Z represents C₁～C₈Alkylidene or C₅～C₁₂Cycloalkylidene, S, SO₂Or a single bond, R represents a substituted or unsubstituted phenyl, methyl, propyl, ethyl, butyl, Cl or Br, and

n represents 0, 1 or 2.

Preferred diphenols are 4, 4 '-dihydroxydiphenyl, 4' -dihydroxydiphenyl sulfide, 1-bis (4-hydroxyphenyl) cyclohexane, 1, 2-bis (4-hydroxyphenyl) benzene, 1, 3-bis (4-hydroxyphenyl) benzene, 1, 4-bis (4-hydroxyphenyl) benzene, bis (4-hydroxyphenyl) methane, 2-bis (4-hydroxyphenyl) propane, 2, 4-bis (4-hydroxyphenyl) -2-methylbutane, 2-bis (3-methyl-4-hydroxyphenyl) propane, 2-bis (3-chloro-4-hydroxyphenyl) -2-propane, bis (3, 5-dimethyl-4-hydroxyphenyl) methane, 2-bis (3, 5-dimethyl-4-hydroxyphenyl) propane, bis (3, 5-dimethyl-4-hydroxyphenyl) -sulfone, bis (4-hydroxyphenyl) sulfone, 1, 2-bis [2- (4-hydroxyphenyl) isopropyl ] -benzene, 1, 3-bis [2- (4-hydroxyphenyl) isopropyl ] benzene, 1, 4-bis [2- (4-hydroxyphenyl) isopropyl ] benzene, 1-bis (4-hydroxyphenyl) -1-phenylethane, 2, 4-bis (4-hydroxyphenyl) -2-methylbutane, 2-bis (3, 5-dichloro-4-hydroxyphenyl) propane, 2-bis (3, 5-dibromo-4-hydroxyphenyl) propane and 1, 1-bis (4-hydroxyphenyl) -3, 3, 5-trimethylcyclohexane.

The most preferred diphenols are 1, 1-bis (4-hydroxyphenyl) -1-phenylethane, 2-bis (4-hydroxyphenyl) propane, 4' -dihydroxydiphenyl, 1-bis (4-hydroxyphenyl) -3, 3, 5-trimethylcyclohexane, 2-bis (3, 5-dibromo-4-hydroxyphenyl) propane and 1, 3-bis [2- (4-hydroxyphenyl) isopropyl ] benzene.

Suitable diphenols also include mixtures of more than one diphenol, where mixtures are used, copolycarbonates are formed. The most preferred mixtures are 1, 3-bis [2- (4-hydroxyphenyl) isopropyl ] benzene, 1-bis (4-hydroxyphenyl) -3, 3, 5-trimethylcyclohexane, 2-bis (4-hydroxyphenyl) propane, 4' -dihydroxybiphenyl and 2, 2-bis (3, 5-dibromo-4-hydroxyphenyl) propane.

In addition, branching agents, for example, compounds containing three functional phenolic hydroxyl groups, may be added. This will obviously lead to branching of the polymer and will increase the non-Newtonian flow behaviour of the polymer. Suitable branching agents include phloroglucinol, 3-bis (3-methyl-4-hydroxyphenyl) -2-oxo-2, 3-indoline, 4, 6-dimethyl-2, 4, 6-tris (4-hydroxyphenyl) heptene-2, 4, 6-dimethyl-2, 4, 6-tris (4-hydroxyphenyl) heptane, 1, 3, 5-tris (4-hydroxyphenyl) benzene, 1, 1, 1-tris (4-hydroxyphenyl) ethane, tris (4-hydroxyphenyl) phenylmethane, 2-bis [4, 4-bis (4-hydroxyphenyl) cyclohexyl ] propane, 2, 4-bis (4-hydroxyphenyl isopropyl) -phenol, 2, 6-bis (2-hydroxy-5' -methylbenzyl) -4-methylphenol, 2- (4-hydroxyphenyl) -2- (2, 4-dihydroxyphenyl) propane, hexa- (4- (4-hydroxyphenylisopropyl) phenyl) -orthoterephthalate, tetrakis (4-hydroxyphenyl) methane, tetrakis (4- (4-hydroxyphenylisopropyl) phenoxy) methane and 1, 4-bis ((4', 4 "-dihydroxytriphenyl) methyl) benzene, isatin biscresol (bisresorcol), pentaerythritol, 2, 4-dihydroxybenzoic acid, 1, 3, 5-trimellitic acid and cyanuric acid.

Suitable catalysts for preparing the polycarbonates according to the invention are, for example, those of the formula (7)

Wherein

R¹、R²、R³And R⁴May represent the same or different C₁～C₁₈Alkylene radical, C₆～C₁₀Aryl or C₅～C₆Cycloalkyl radicals, and

X^-may represent an anion in which the corresponding acid-base pairHaving a pK of < 11_bAnd in addition a cocatalyst.

Preferred catalysts are fluorinated (tetraphenylphosphonium), tetraphenylphosphonium tetraphenylborate and tetraphenylphosphonium phenolate. Most preferred is a mixture of tetraphenylphosphonium phenolate and sodium phenolate, in the presence of 210500ppb of sodium. The preferred amount of phosphonium salt catalyst is 10^-2～10^-8The most preferred amount of catalyst is 10 moles per mole of diphenol^-4～10^-6Moles per mole of diphenol. Additional cocatalysts are used on the basis of the addition of the phosphonium salt in order to increase the polymerization rate. Such promoters include amine salts, alkali metal and alkaline earth metal salts, for example, hydroxides, alkoxides and phenoxides of lithium, sodium and potassium. Most preferred are sodium hydroxide and sodium phenolate. The amount of cocatalyst used may be in the range 201 to 10,000ppb, preferably 220 to 1500ppb, most preferably 240 to 500ppb, in each case calculated as sodium.

The polycarbonate can be produced under reaction conditions carried out at a temperature of 150 ℃ to 400 ℃, the residence time of each stage can be between 15min and 5h, and the pressure is between 0.1MPa and 1Pa (1000 to 0.01 mbar).

The present invention also provides polycarbonate compositions comprising the polycarbonates according to the invention, and also moldings comprising such compositions.

The compositions of the invention may comprise, in addition to the polycarbonate or polyester carbonate, further polymer components and conventional additives. Possible polymer components are, for example, styrene/acrylic/nitrile terpolymers (SAN), acrylic/butadiene/styrene terpolymers (ABS), poly (methyl methacrylate) (PMMA), fluorinated Polyolefins (PTFE), polyphenylstyrene (PPS), polyolefins such as polyethylene, polypropylene and ethylene-propylene rubbers, epoxy resins, polyesters such as polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polycyclohexanedimethanol, copolyesters of ethylene glycol and cyclohexenedimethanol terephthalic acid in a ratio of the two components of 1: 4 (PCTG), copolyesters of ethylene glycol and cyclohexenedimethanol terephthalic acid in a ratio of the two components of 4: 1 (PETG) and also other polycarbonates produced by the interfacial process and even mixtures of the above-mentioned components. Further additives include mold release agents, stabilizers, antioxidants, flame retardants, colorants and pigments, antistatic agents, nucleating agents, anti-drip agents, as well as organic and inorganic fillers and reinforcing agents.

The polycarbonates according to the invention are preferably present in the compositions according to the invention in an amount of from 5 to 95 wt.%, particularly preferably from 10 to 90 wt.%, most preferably from 20 to 80 wt.%, referred to the weight of the composition. The composition of the invention preferably comprises the further polymer component in an amount of from 1 to 60% by weight, particularly preferably from 1 to 40% by weight, most preferably from 2 to 30% by weight, relative to the weight of the composition.

The compositions may contain up to 60% by weight, preferably from 10 to 40% by weight, of inorganic materials such as fillers and/or reinforcing agents, relative to the filled or reinforced molding compositions. The flame retardant is present in the composition according to the invention in an amount of up to 35% by weight, preferably 10 to 25% by weight, relative to the weight of the composition.

These and further components or additives which can be contained in the compositions according to the invention, in addition to the polycarbonate/polyestercarbonate, are exemplified below.

These substances are found in numerous publications, for example in the handbook of plastics additives, John Murphy, 1999, and are commercially available.

1. Suitable antioxidants are, for example:

alkylated monophenols, for example 2, 6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4, 6-dimethylphenol, 2, 6-di-tert-butyl-4-ethylphenol, 2, 6-di-tert-butyl-4-n-butylphenol, 2, 6-di-tert-butyl-4-isobutylphenol, 2, 6-dicyclopentyl-4-methylphenol, 2- (. alpha. -methylcyclohexyl) -4, 6-dimethylphenol, 2, 6-dioctadecyl-4-methylphenol, 2, 4, 6-tricyclohexylphenol, 2, 6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which can be linear or branched in the side chain, for example, 2, 6-dinonyl-4-methylphenol, 2, 4-dimethyl-6- (1 '-methylundec-1' -yl) phenol, 2, 4-dimethyl-6- (1 '-methylheptadec-1' -yl) phenol, 2, 4-dimethyl-6- (1 '-methyltridec-1' -yl) phenol.

Alkylthiomethylphenols, for example 2, 4-dioctylthiomethyl-6-tert-butylphenol, 2, 4-dioctylthiomethyl-6-methylphenol, 2, 4-dioctylthiomethyl-6-ethylphenol, 2, 6-di-dodecylthio-methyl-4-nonylphenol.

Hydroquinones and alkylated hydroquinones, for example 2, 6-di-tert-butyl-4-methoxyphenol, 2, 5-di-tert-butylhydroquinone, 2, 5-di-tert-amylhydroquinone, 2, 6-diphenyl-4-octadecyloxyphenol, 2, 6-di-tert-butylhydroquinone, 2, 5-di-tert-butyl-4-hydroxyanisole, 3, 5-di-tert-butyl-4-hydroxyphenyl stearate and bis (3, 5-di-tert-butyl-4-hydroxyphenyl) adipate.

Tocopherols, e.g., alpha-tocopherol, beta-tocopherol, gamma-tocopherol, delta-tocopherol and mixtures thereof (vitamin E).

Hydroxylated thiodiphenyl ethers, for example 2, 2 '-thiobis (6-tert-butyl-4-methylphenol), 2, 2' -thiobis (4-octylphenol), 4 '-thiobis (6-tert-butyl-3-methylphenol), 4' -thiobis (6-tert-butyl-2-methylphenol), 4 '-thiobis (3, 6-di-sec-amylphenol), 4' -bis (2, 6-dimethyl-4-hydroxyphenol) disulfide.

Alkylidenebisphenols, for example 2, 2 ' -methylenebis (6-tert-butyl-4-methylphenol), 2, 2 ' -methylenebis (6-tert-butyl-4-ethylphenol), 2, 2 ' -methylenebis [ 4-methyl-6- (. alpha. -methylcyclohexyl) phenol ], 2, 2 ' -methylenebis (4-methyl-6-cyclohexylphenol), 2, 2 ' -methylenebis (6-nonyl-4-methylphenol), 2, 2 ' -methylenebis (4, 6-di-tert-butylphenol), 2, 2 ' -ethylenebis (6-tert-butyl-4-isobutylphenol), 2, 2 '-methylenebis [6- (. alpha. -methylbenzyl) -4-nonylphenol ], 2' -methylenebis [6- (. alpha.,. alpha. -dimethylbenzyl) -4-nonylphenol ], 4 '-methylenebis (2, 6-di-tert-butylphenol), 4' -methylenebis (6-tert-butyl-2-methylphenol), 1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2, 6-bis (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1, 3-tris (5-tert-butyl-4-, 1, 1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecylmercaptobutane, ethylene glycol-bis [3, 3-bis (3 '-tert-butyl-4' -hydroxy-phenyl) butyrate ], bis (3-tert-butyl-4-hydroxy-5-methylphenyl) -dicyclopentadiene, bis [2- (3 '-tert-butyl-2' -hydroxy-5 '-methylbenzyl) -6-tert-butyl-4-methylphenyl ] -terephthalate, 1-bis (3, 5-dimethyl-2-hydroxyphenyl) butane, 2-bis (3, 5-di-tert-butyl-4-hydroxyphenyl) propane, ethylene glycol-bis [3, 3' -di (3 '-tert-butyl-4' -hydroxy-phenyl) butyrate ], bis (3-tert-butyl-4-hydroxyphenyl) propane, ethylene glycol-bis [2- (3, 2, 2-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -4-n-dodecylmercaptobutane, 1, 5, 5-tetrakis (5-tert-butyl-4-hydroxy-2-methylphenyl) -pentane.

O-, N-and S-benzyl compounds, for example 3, 5,3 ', 5 ' -tetra-tert-butyl-4, 4 ' -dihydroxydibenzyl ether, octadecyl-4-hydroxy-3, 5-dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy-3, 5-di-tert-butylbenzylmercaptoacetate, tris (3, 5-di-tert-butyl-4-hydroxybenzyl) amine, bis (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) dithioterephthalate, bis (3, 5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl-3, 5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.

Hydroxybenzylated malonates, for example dioctadecyl-2, 2-bis (3, 5-di-tert-butyl-2-hydroxybenzyl) malonate, dioctadecyl-2- (3-tert-butyl-4-hydroxy-5-methylbenzyl) malonate, didodecylmercaptoethyl-2, 2-bis (3, 5-di-tert-butyl-4-hydroxybenzyl) malonate-, bis [4- (1, 1, 3, 3-tetramethylbutyl) phenyl ] -2, 2-bis (3, 5-di-tert-butyl-4-hydroxybenzyl) malonate.

Aromatic hydroxybenzyl compounds, for example 1, 3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) -2, 4, 6-trimethylbenzene, 1, 4-bis (3, 5-di-tert-butyl-4-hydroxybenzyl) -2, 3, 5, 6-tetramethylbenzene, 2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) phenol.

Triazine Compounds, for example 2, 4-bis (octylmercapto) -6- (3, 5-di-tert-butyl-4-hydroxyanilino) -1, 3, 5-triazine, 2-octylmercapto-4, 6-bis (3, 5-di-tert-butyl-4-hydroxyphenoxy) -1, 3, 5-triazine, 2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxyphenoxy) -1, 2, 3-triazine, 1, 3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1, 3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) isocyanurate, 2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxyphenylethyl) -1, 3, 5-triazine, 1, 3, 5-tris (3, 5-di-tert-butyl-4-hydroxyphenylpropionyl) -hexahydro-1, 3, 5-triazine, 1, 3, 5-tris (3, 5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.

Acylaminophenols, for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl-N- (3, 5-di-tert-butyl-4-hydroxyphenyl) carbamate.

Esters of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid with monohydric or polyhydric alcohols, for example with methanol, ethanol, N-octanol, isooctanol, octadecanol, 1, 6-hexanediol, 1, 9-nonanediol, ethylene glycol, 1, 2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N' -bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane.

Esters of beta- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with monohydric or polyhydric alcohols, for example with methanol, ethanol, N-octanol, isooctanol, octadecanol, 1, 6-hexanediol, 1, 9-nonanediol, ethylene glycol, 1, 2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N' -bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane.

Esters of beta- (3, 5-dicyclohexyl-4-hydroxyphenyl) propionic acid with monohydric or polyhydric alcohols, for example with methanol, ethanol, octanol, octadecanol, 1, 6-hexanediol, 1, 9-nonanediol, ethylene glycol, 1, 2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N' -bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane.

Esters of 3, 5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono-or polyhydric alcohols, for example with methanol, ethanol, octanol, octadecanol, 1, 6-hexanediol, 1, 9-nonanediol, ethylene glycol, 1, 2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N' -bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane.

Amides of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid, for example N, N '-bis (3, 5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamide, N, N' -bis (3, 5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylenediamide, N, N '-bis (3, 5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazide, N, N' -bis [2- (3- [3, 5-di-tert-butyl-4-hydroxyphenyl ] propionyloxy) ethyl ] oxamide (Naugard * XL-1, supplied by Uniroyal).

1.17 ascorbic acid (vitamin C)

Amine-type antioxidants, for example N, N '-diisopropyl-p-phenylenediamine, N, N' -di-sec-butyl-p-phenylenediamine, N, N '-bis (1, 4-dimethylpentyl) -p-phenylenediamine, N, N' -bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N, N '-bis (1-methylheptyl) -p-phenylenediamine, N, N' -dicyclohexyl-p-phenylenediamine, N, N '-diphenyl-p-phenylenediamine, N, N' -bis (2-naphthyl) -p-phenylenediamine, N-isopropyl-N '-phenyl-p-phenylenediamine, N- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine, N, N '-di-isopropyl-p-phenylenediamine, N, N' -di-tert-phenylenediamine, N, N '-di-methyl-3-pentyl-p-phenylenediamine, N, N' -, N- (1-methylheptyl) -N ' -phenyl-p-phenylenediamine, N-cyclohexyl-N ' -phenyl-p-phenylenediamine, 4- (p-toluenesulfonamide) diphenylamine, N ' -dimethyl-N, N ' -di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyl-diphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N- (4-tert-octylphenyl) -1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, for example p, p ' -di-tert-octyldiphenylamine, 4-N-butylamino-phenol, 4-butylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, N-cyclohexylaminodiphenylamine, N-cyclohexyldiphenylamine, N-propyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, 4-octadecanoylaminophenol, bis (4-methoxybenzene) amine, 2, 6-di-tert-butyl-4-dimethylaminomethylphenol, 2, 4 ' -diaminodiphenylmethane, 4 ' -diaminodiphenylmethane, N, N, N ', N ' -tetramethyl-4, 4 ' -diaminodiphenylmethane, 1, 2-bis [ (2-methylphenyl) amino ] ethane, 1, 2-bis (phenylamino) propane, (o-tolyl) biguanide, bis [4- (1 ', 3 ' -dimethylbutyl) phenyl ] amine, tert-octylated N-phenyl-1-naphthylamine, mixtures of monoalkylated and dialkylated tert-butyl/tert-octyldiphenylamines, mixtures of monoalkylated and dialkylated nonyldiphenylamines, A mixture of monoalkylated and dialkylated dodecyldiphenylamines, a mixture of monoalkylated and dialkylated isopropyl/isohexyldiphenylamines, a mixture of monoalkylated and dialkylated tert-butyldiphenylamines, 2, 3-dihydro-3, 3-dimethyl-4H-1, 4-benzothiazine, phenothiazine, a mixture of monoalkylated and dialkylated tert-butyl/tert-octylphenothiazines, a mixture of monoalkylated and dialkylated tert-octylphenothiazines, N-allylphenothiazine, N, N, N ', N' -tetraphenyl-1, 4-diaminobut-2-ene, N, N-bis (2, 2,6, 6-tetramethylpiperidin-4-yl-hexamethylenediamine, bis (2, 2,6, 6-tetramethylpiperidin-4-yl) sebacate, 2,6, 6-tetramethylpiperidin-4-one, 2,6, 6-tetramethylpiperidin-4-ol. Either a single compound or a mixture thereof may be used.

1.19 suitable thiosynergists are, for example, dilauryl thiodipropionate and/or distearyl thiodipropionate.

2. The UV absorbers and light stabilizers may be used in the compositions according to the invention in amounts of from 0.1 to 15% by weight, preferably from 3 to 8% by weight, relative to the weight of the composition. Suitable UV absorbers and light stabilizers are, for example:

2.1.2- (2 '-hydroxyphenyl) benzotriazoles, for example 2- (2' -hydroxy-5 '-methylphenyl) benzotriazole, 2- (3', 5 '-di-tert-butyl-2' -hydroxyphenyl) benzotriazole, 2- (5 '-tert-butyl-2' -hydroxyphenyl) benzotriazole, 2- (2 '-hydroxy-5' - (1, 1, 3, 3-tetramethyl-butyl) phenyl) benzotriazole, 2- (3 ', 5' -di-tert-butyl-2 '-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3' -tert-butyl-2 '-hydroxy-5' -methylphenyl) -5-chlorobenzotriazole, 2- (3 '-sec-butyl-5' -tert-butyl-2 '-hydroxyphenyl) benzotriazole, 2- (2' -hydroxy-4 '-octyloxyphenyl) benzotriazole, 2- (3', 5 '-di-tert-amyl-2' -hydroxyphenyl) benzotriazole, 2- (3 ', 5' -bis (. alpha.,. alpha. -dimethylbenzyl) -2 '-hydroxyphenyl) benzotriazole, 2- (3' -tert-butyl-2 '-hydroxy-5' - (2-octyloxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3 '-tert-butyl-5' - [2- (2-ethylhexyloxy) carbonylethyl ] benzotriazole]-2 '-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3' -tert-butyl-2 '-hydroxy-5' - (2-methoxycarbonylethyl) -phenyl) -5-chlorobenzotriazole, 2- (3- '-tert-butyl-2' -hydroxy-5 '- (2-methoxycarbonylethyl) phenyl) benzotriazole, 2- (3' -tert-butyl-2 '-hydroxy-5' - (2-octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3 '-tert-butyl-5' - [2- (2-ethylhexyloxy) carbonylethyl]-2 '-hydroxyphenyl) benzotriazole, 2- (3' -dodecyl-2 '-hydroxy-5' -methylphenyl) benzotriazole, 2- (3 '-tert-butyl-2' -hydroxy-5 '- (2-isooctyloxycarbonylethyl) phenyl) benzotriazole, 2' -methylene-bis [4- (1, 1, 3, 3-tetramethylbutyl) -6-benzotriazol-2-ylphenol](ii) a 2[3 ' -tert-butyl-5 ' - (2-methoxycarbonylethyl) -2 ' -hydroxyphenyl]-transesterification products of 2H-benzotriazole with polyethylene glycol 300; [ R-CH₂CH₂-COO-CH₂CH₂]₂Wherein R is 3 '-tert-butyl-4' -hydroxy-5 '-2H-benzotriazol-2-yl-phenyl, 2- [ 2' -hydroxy-3 '- (α, α -dimethylbenzyl) -5' - (1, 1, 3, 3-tetramethylbutyl) phenyl]Benzotriazole, 2- [2 ' -hydroxy-3 ' - (1, 1, 3, 3-tetramethylbutyl) -5 ' - (alpha, alpha-dimethylbenzyl) phenyl]Benzotriazole.

2.2.2-hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4, 2 ', 4' -trihydroxy and 2 '-hydroxy-4, 4' -dimethoxy derivatives.

Esters of substituted and unsubstituted benzoic acids, for example 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, bis (benzoyl) resorcinol, bis (4-tert-butylbenzoyl) resorcinol, benzoyl resorcinol, 2, 4-di-tert-butylphenyl 3, 5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3, 5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3, 5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4, 6-di-tert-butylphenyl 3, 5-di-tert-butyl-4-hydroxybenzoate.

Acrylates, for example ethyl α -cyano- β, β -diphenylacrylate, isooctyl α -cyano- β, β -diphenylacrylate, methyl α -carbomethoxycinnamate, methyl α -cyano- β -methyl-p-ester methoxycinnamate butyl α -cyano- β -methyl-p-methoxycinnamate, methyl α -carbomethoxy-p-methoxycinnamate and N- (β -carbomethoxy- β -cyanovinyl) -2-methyldihydroindole.

Nickel compounds, for example nickel complexes of 2, 2' -thiobis [4- (1, 1, 3, 3-tetramethylbutyl) phenol ], such as the 1: 1 complex or the 1: 2 complex, with or without additional ligands such as N-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of monoalkyl esters, e.g. of the methyl or ethyl ester of 4-hydroxy-3, 5-di-tert-butylbenzylphosphonic acid, nickel complexes of ketoximes, such as of 2-hydroxy-4-methylphenyl undecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands.

Sterically hindered amines, for example bis (2, 2,6, 6-tetramethyl-4-piperidyl) sebacate, bis (2, 2,6, 6-tetramethyl-4-piperidyl) succinate, bis (1, 2, 2,6, 6-pentamethyl-4-piperidyl) sebacate, bis (1-octyloxy-2, 2,6, 6-tetramethyl-4-piperidyl) sebacate, bis (1, 2, 2,6, 6-pentamethyl-4-piperidyl), n-butyl-3, 5-di-tert-butyl-4-hydroxybenzylmalonate, condensation products of 1- (2-hydroxyethyl) -2, 2,6, 6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensates of N, N '-bis (2, 2,6, 6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-tert-octylamino-2, 6-dichloro-1, 3, 5-triazine, tris (2, 2,6, 6-tetramethyl-4-piperidylnitrilotriacetate, tetrakis (2, 2,6, 6-tetramethyl-4-piperidyl) -1, 2, 3, 4-butanetetracarboxylate, 1' - (1, 2-ethanediyl) bis (3, 3, 5, 5-tetramethylpiperazinone), 4-benzoyl-2, 2,6, 6-tetramethylpiperidine, 4-octadecyloxy-2, 2,6, 6-tetramethylpiperidine, bis (1, 2, 2,6, 6-pentamethylpiperidyl) -2-N-butyl-2- (2-hydroxy-3, 5-di-tert-butylbenzyl) malonate, 3-N-octyl-7, 7, 9, 9-tetramethyl-1, 3, 8-triazaspiro [4.5] decane-2, 4-dione, bis (1-octyloxy-2, 2,6, 6-tetramethylpiperidyl) sebacate, bis (1-octyloxy-2, 2,6, 6-tetramethylpiperidyl) succinate, N' -bis (2, 2,6, 6-tetramethyl-4-piperidyl) hexamethylenediamine and linear or cyclic condensation product of 4-morpholinyl-2, 6-dichloro-1, 3, 5-triazine, A condensation product of 2-chloro-4, 6-bis (4-n-butylamino-2, 2,6, 6-tetramethylpiperidyl) -1, 3, 5-triazine and 1, 2-bis (3-aminopropylamino) ethane, a condensation product of 2-chloro-4, 6-bis (4-n-butylamino-1, 2, 2,6, 6-pentamethylpiperidyl) -1, 3, 5-triazine and 1, 2-bis (3-aminopropylamino) ethane, a condensation product of 8-acetyl-3-dodecyl-7, 7, 9, 9-tetramethyl-1, 3, 8-triazaspiro [4, 5] decane-2, 4-dione, 3-dodecyl-1- (2, 6, 6-tetramethyl-4-piperidyl) pyrrolidine-2, 5-dione, 3-dodecyl-1- (1, 2, 2,6, 6-pentamethyl-4-piperidyl) pyrrolidine-2, 5-dione, a mixture of 4-hexadecyloxy-and 4-octadecyloxy-2, 2,6, 6-tetramethylpiperidine, a condensation product of N, N' -bis (2, 2,6, 6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-cyclohexylamino-2, 6-dichloro-1, 3, 5-triazine, a condensation product of 1, 2-bis (3-aminopropylamino) ethane and 2, 4, 6-trichloro-1, 3, 5-triazine, or even 4-butylamino-2, 2,6, 6-tetramethylpiperidine (CAS catalog [136504-96-6 ]); n- (2, 2,6, 6-tetramethyl-4-piperidyl) -N-dodecylsuccinimide, N- (1, 2, 2,6, 6-pentamethyl-4-piperidyl) -N-dodecylsuccinimide, 2-undecyl-7, 7, 9, 9-tetramethyl-1-oxa-3, 8-diaza-4-oxospiro [4.5] decane, a reaction product of 7, 7, 9, 9-tetramethyl-2-cycloundecyl-1-oxa-3, 8-diaza-4-oxospiro [4.5] decane and epichlorohydrin, 1-bis (1, 2, 2,6, 6-pentamethyl-4-piperidyl-oxycarbonyl) -2- (4-methoxyphenyl) ethylene, N, N '-bis (formyl) -N, N' -bis (2, 2,6, 6-tetramethyl-4-piperidinyl) hexamethylenediamine, the diester of 4-methoxymethylenemalonic acid with 1, 2, 2,6, 6-pentamethyl-4-hydroxypiperidine, poly [ methylpropyl-3-oxo-4- (2, 2,6, 6-tetramethyl-4-piperidinyl) ] siloxane; reaction products of maleic anhydride-alpha-olefin copolymers with 2, 2,6, 6-tetramethyl-4-aminopiperidine or 1, 2, 2,6, 6-pentamethyl-4-aminopiperidine.

Oxamides, for example 4, 4 ' -dioctyloxyoxanilide, 2 ' -diethoxyoxanilide, 2 ' -dioctyloxy-5, 5 ' -di-tert-butoxanilide, 2 ' -didodecyloxy-5, 5 ' -di-tert-butoxanilide, 2-ethoxy-2 ' -ethyloxanilide, N, oxanilide, 2-ethoxy-5-tert-butyl-2 ' -ethyloxanilide and mixtures thereof with 2-ethoxy-2 ' -ethyl-5, 4 ' -di-tert-butyloxanilide, mixtures of o-and p-methoxy-disubstituted oxanilides and mixtures of o-and p-ethoxy-disubstituted oxanilides.

2.8.2- (2-hydroxyphenyl) -1, 3, 5-triazines, for example 2, 4, 6-tris (2-hydroxy-4-octyloxyphenyl) -1, 3, 5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1, 3, 5-triazine, 2- (2, 4-dihydroxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1, 3, 5-triazine, 2, 4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2, 4-dimethylphenyl) -1, 3, 5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4, 6-bis (4-methylphenyl) -1, 3, 5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1, 3, 5-triazine, 2- (2-hydroxy-4-tridecyloxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1, 3, 5-triazine, 2- [ 2-hydroxy-4- (2-hydroxy-3-butoxypropoxy) phenyl ] -4, 6-bis (2, 4-dimethyl) -1, 3, 5-triazine, 2- [ 2-hydroxy-4- (2-hydroxy-3-octyloxypropoxy) phenyl ] -4, 6-bis (2, 4-dimethyl) -1, 3, 5-triazine, 2- [ 4-dodecyloxy, tridecyloxy-2-hydroxypropoxy ] -2-hydroxyphenyl ] -4, 6-bis (2, 4-dimethylphenyl) -1, 3, 5-triazine, 2- [ 2-hydroxy-4- (2-hydroxy-3-dodecyloxypropoxy) phenyl ] -4, 6-bis (2, 4-dimethylphenyl) -1, 3, 5-triazine, 2- (2-hydroxy-4-hexyloxy) phenyl-4, 6-diphenyl-1, 3, 5-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4, 6-diphenyl-1, 3, 5-triazine, 2, 4, 6-tris [ 2-hydroxy-4- (3-butoxy-2-hydroxypropoxy) phenyl ] -1, 3, 5-triazine, 2- (2-hydroxyphenyl) -4- (4-methoxyphenyl) -6-phenyl-1, 3, 5-triazine, 2- { 2-hydroxy-4- [3- (2-ethylhexyl-1-oxo) -2-hydroxypropoxy ] phenyl) -4, 6-bis (2, 4-dimethylphenyl) -1, 3, 5-triazine.

Both single compounds and mixtures thereof may be used.

3. Suitable metal deactivators are, for example, N ' -diphenyloxamide, N-salicylal-N ' -salicyloyl hydrazine, N ' -bis (salicyloyl) hydrazine, N ' -bis (3, 5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1, 2, 4-triazole, bis (benzylidene) oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N ' -diacetyladipoyl dihydrazide, N ' -bis (salicyloyl) oxalyl dihydrazide, N ' -bis (salicyloyl) thiopropionyl dihydrazide.

Both single compounds and mixtures thereof may be used.

4. Phosphites and phosphonites suitable for use as heat stabilizers include, for example, triphenyl phosphite, diphenyl phosphite. Alkyl esters, phenyl phosphites. Dialkyl esters, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, dioctadecyl pentaerythritol diphosphite, tris (2, 4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecyl pentaerythritol diphosphite, bis (2, 4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite, bis (2, 4, 6-tris (tert-butylphenyl) pentaerythritol diphosphite, trioctadecyl sorbitol triphosphite, tetrakis (2, 4-di-tert-butylphenyl) -4, 4' -biphenylene diphosphonite, 6-isooctyloxy-2, 4, 8, 10-tetra-tert-butyl-12H-dibenzo [ d, g ] -1, 3, 2-dioxaphospholane (phospholane), 6-fluoro-2, 4, 8, 10-tetra-tert-butyl-12-methyldibenzo [ d, g ] -1, 3, 2-dioxaphospholane (phospholane), bis (2, 4-di-tert-butyl-6-methylphenyl) methyl phosphite, bis (2, 4-di-tert-butyl-6-methylphenyl) ethyl phosphite, 6-fluoro-2, 4, 8, 10-tetra-tert-butyl-12-methyldiphenyl [ d, g ] -1, 3, 2-dioxaphospholane (phospholane), 2, 2 ', 2 "-nitrilo [ triethyltris (3, 3', 5, 5 '-tetra-tert-butyl-1, 1' -biphenyl-2, 2 '-diyl) phosphite ], 2-ethylhexyl (3, 3', 5, 5 '-tetra-tert-butyl-1, 1, -biphenyl-2, 2' -diyl) phosphite, 5-butyl-5-ethyl-2- (2, 4, 6-tri-tert-butylphenoxy) -1, 3, 2-dioxaphospholane (phosphirane). Both single compounds and mixtures thereof may be used.

Particularly preferred are tris (2, 4-di-tert-butylphenyl) phosphite (Irgafos * 168, Ciba-Geigy), triphenylphosphine or (2, 4, 6-tri-tert-butylphenyl) - (2-butyl-2-ethylpropane-1, 3-diyl) phosphite (Ultranox 641 * GE specialty Chemicals).

Examples of suitable phosphites and phosphonites are also:

5. suitable peroxide traps are, for example, esters of beta-thiodipropionic acid, for example, the lauryl, octadecyl, myristyl or tridecyl ester, the zinc salt of mercaptobenzimidazole or 2-mercaptobenzimidazole, dithiocarbamic acid (dibutyl zinc), dioctadecyl disulfide, pentaerythritol tetradodecylmercapto propionate. Both single compounds and mixtures thereof may be used.

6. Suitable basic co-stabilisers are, for example, melamine, poly (vinylpyrrolidone), dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or zinc pyrocatecholate. Both single compounds and mixtures thereof may be used.

7. Suitable nucleating agents are, for example, inorganic substances, for example talc, metal oxides such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates, preferably of alkaline earth metals; organic compounds such as mono-or polycarboxylic acids and their salts, for example 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds, for example, ionic copolymers (ionomers). Particularly preferably 1, 3: 2, 4-bis (3 ', 4' -dimethylbenzylidene) sorbitol, 1, 3: 2, 4-bis (p-methyldibenzylidene) sorbitol and 1, 3: 2, 4-bis (benzylidene) sorbitol. Both single compounds and mixtures thereof may be used.

8. Suitable fillers and reinforcing agents are, for example, calcium carbonate, silicates, glass fibres, glass bulbs, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wollastonite, sawdust and powders or fibres of other natural products, synthetic fibres. Both single compounds and mixtures thereof may be used.

9. Further suitable additives are, for example, plasticizers, lubricants, emulsifiers, pigments, viscosity regulators, catalysts, flow auxiliaries, optical brighteners, flame retardants, antistatic agents and blowing agents.

10. Suitable benzofuranones and indolinones are, for example, those disclosed in U.S. Pat. No. 4,325,863, U.S. Pat. No. 4,338,244, U.S. Pat. No. 5,175,312, U.S. Pat. No. 5,216,052, U.S. Pat. No. 5,252,643, DE-A-4316611, DE-A-4316622, DE-A-1684376, EP-A-0589839 or EP-A-0591102 or 3- [4- (2-acetoxyethoxy) phenyl ] -5, 7-di-tert-butylbenzofuran-2-one, 5, 7-di-tert-butyl 3- [4- (2-stearoyloxyethoxy) phenyl ] -benzofuran-2-one, 3' -bis- [5, 7-di-tert-butyl 3- (4- [ 2-hydroxyethoxy ] phenyl) -benzofuran-2-one ] (B), 5, 7-di-tert-butyl-3- (4-ethoxyphenyl) benzofuran-2-one, 3- (4-acetoxy-3, 5-dimethylphenyl) -5, 7-di-tert-butylbenzofuran-2-one, 3- (3, 5-dimethyl-4-pivaloyloxyphenyl) -5, 7-di-tert-butylbenzofuran-2-one, 3- (3, 4-dimethylphenyl) -5, 7-di-tert-butylbenzofuran-2-one, 3- (2, 3-dimethylphenyl) -5, 7-di-tert-butylbenzofuran-2-one, lactone antioxidants, for example,

these compounds act, for example, as antioxidants. Both single compounds and mixtures thereof may be used.

11. Suitable fluorescent plasticizers are listed in the handbook of Plastic additives, eds: gachter and H.Muller, Hanser Press, third edition, 1990, pp.775-789.

12. Suitable mould release agents are esters of aliphatic acids and alcohols, for example pentaerythritol tetrastearate and glycerol monostearate, which may be used individually or in mixtures, preferably in amounts of from 0.02 to 1% by weight, relative to the weight of the composition.

13. Suitable flame retardant additives are phosphate esters, i.e.triphenyl phosphate, resorcinol diphosphate, bromine-containing compounds such as brominated phosphate esters, brominated oligocarbonates and polycarbonates, as well as salts such as C₄F₉SO₃ ^-Na⁺。

14. Suitable impact modifiers are: butadiene rubber to which styrene-acrylonitrile or methyl methacrylate is grafted; ethylene-propylene rubber onto which maleic anhydride is grafted; ethyl acrylate and butyl acrylate rubbers onto which methyl methacrylate or styrene-acrylonitrile is grafted; interpenetrating siloxane and acrylate networks onto which methyl methacrylate or styrene-acrylonitrile is grafted.

15. Suitable polymers are SAN, ABS, PMMA, PTFE, PSU, PPS, polyolefins such as polyethylene, polypropylene and ethylene-propylene rubber, epoxy resins, polyesters such as PBT, PET, PCT, PCTG and PETG and also other polycarbonates produced by the interfacial process.

16. Suitable antistatic agents are sulfonates, e.g. C₁₂H₂₅SO^3-Or C₈F₁₇SO^3-The tetraethylammonium salt of (a).

17. Suitable colorants are pigments and organic and inorganic colorants.

18. Compounds containing epoxy groups, for example, 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexylcarboxylate, copolymers of glycidyl methacrylate and epoxy silanes.

19. Compounds containing anhydride groups, for example maleic anhydride, succinic anhydride, benzoic anhydride and phthalic anhydride.

The compounds of items 18 and 19 are useful as melt stabilizers. They may be used alone or as a mixture.

The compositions according to the invention (molding compositions) are prepared by mixing the individual components in a known manner and melt-compounding or melt-extruding the mixture obtained at a temperature of about 200 ℃, for example at a temperature of from 200 ℃ to 300 ℃ in conventional equipment such as internal mixers and extruders and twin-screw extruders. The mixing of the individual components can be carried out successively or simultaneously, more particularly at about 20 c (room temperature) and also at higher temperatures.

The molding compositions of the invention can be used for the production of molded objects of any type. These moldings can be produced by injection molding, extrusion molding and blow molding. Another type of processing is the production of molded bodies by deep-drawing of previously produced sheets and films.

Examples of the mouldings according to the invention include profiles, films, all types of cast parts, for example for domestic appliances, if juicers, coffee machines, mixers; office equipment, such as monitors, printers, copiers; sheets, pipes, electrical installation bushings, profiles for windows, doors and building engineering, interior fittings and exterior applications; in the field of electrotechnical technology, for example for switches and plugs. In addition, the moldings of the invention can be used for interior fittings and structural parts of rail vehicles, ships, aircraft, buses and other vehicles and body parts of motor vehicles.

The mouldings according to the invention may be transparent or opaque. Furthermore, mouldings include, in particular, optical and magneto-optical data storage media, such as minidiscs, Compact Discs (CD) or Digital Versatile Discs (DVD), food and beverage packaging, optical lenses and prisms, lighting panes, motor vehicle light panes, architectural and motor vehicle glazings, other types of glazings, for example for greenhouses, so-called reinforced sandwich panels or hollow panels. The following examples serve to illustrate the invention in more detail.

Examples

The polymers of examples 1 to 3 were prepared by melt polymerization of diphenyl carbonate and bisphenol A in the molten state, using tetraphenylphosphonium phenolate and 250ppb sodium phenolate as catalysts.

The monomer and catalyst amounts are shown in Table 1. The reaction conditions are given in table 2. The measured relative solution viscosity, Yellowness Index (YI), melt viscosity, shear-thinning ratio and amount of polyfunctional compound used are given in Table 3.

Comparative examples 1, 2 and 3 relate to linear polycarbonates produced according to the conventional interfacial polymerization process. Such polycarbonates are commercially available from the Bayer corporation under the tradenames Makrolon * 2808, 2408, and 3108. The polymers of comparative examples 4 and 5 were branched polycarbonates produced using the interfacial polymerization method. Corresponding products are sold by the Bayer company under the trade names Makrolon * 1243 and 1239. Comparative examples 7, 8 and 9 were prepared by reacting diphenyl carbonate and bisphenol a in the molten state with phenol tetraphenylphosphonium salt as the catalyst. The polycarbonate of example 6 was prepared by reacting diphenyl carbonate and bisphenol A in the molten state with tetraphenylphosphonium phenolate and 100ppb sodium phenolate, calculated as sodium, as catalysts.

The polymerization reaction may be carried out using conventional transesterification vessels of materials suitable for heating and evacuation and providing sufficiently long mixing and residence times.

The relative viscosity is determined as a 0.5% solution in dichloromethane at 20 ℃.

The Yellowness Index (YI) is determined by the CIELAB method on 4mm thick injection-molded specimens. The injection molding was carried out at 270 ℃, 300 ℃ and 330 ℃.

The melt viscosity is determined at 280 ℃ using the test method according to ISO 11443. The non-Newtonian flow behaviour is quantified by calculating the shear-thinning ratio. The shear thinning ratio is 50s^-1The melt viscosity at shear rate of (3) divided by the melt viscosity at 5,000s^-1Is calculated from the melt viscosity at the shear rate of (2).

The amount of the polyfunctional compound is determined by separating the monomeric compound of the polycarbonate after complete hydrolysis by HPLC (high pressure liquid chromatography). These compounds were identified using magnetic resonance spectroscopy techniques.

TABLE 1

Examples of the invention	V6	V7	V8	V9	1	2	3
								DPC，Mol	1.18	1.173	1.187	1.168	1.178	1.214	1.209
BPA，Mol	1.0	1.0	1.0	1.0	1.0	1.0	1.0
								Sodium phenolate (ppb) as sodium	100	0.0	0.0	0.0	250	250	250
Tetraphenylphosphonium phenolate, mol	0.00004	0.00004	0.00004	0.00004	0.00004	0.00004	0.00004

DPC: diphenyl carbonate; BPA: bisphenol A

TABLE 2

Reaction conditions of comparative examples 6 to 9 and examples 1 to 3	Time (mim)	Temperature (. degree.C.)	Pressure (mbar)
				Precondensation	45	190	1000
Reactor I	20	190	200
				Reactor II	20	230	80
Reactor III	10	250	50
				Reactor IV	10	270	25
Reaction conditions of comparative example 6
				Evaporator I	45	275	7.4
Evaporator II	130	310	1.40
				Reaction conditions of comparative example 7
Evaporator I	45	275	7.3
				Evaporator II	130	312	1.00
Reaction conditions of comparative example 8
				Evaporator I	45	275	5.5
Evaporator II	130	312	0.5
				Reaction conditions of comparative example 9
Evaporator I	45	275	7.3
				Evaporator II	130	312	0.98
Reaction conditions of example 1
				Evaporator I	45	275	8.5
Evaporator II	120	310	2.25
				Reaction conditions of example 2
Evaporator I	45	275	6.5
				Evaporator II	120	310	0.90
Reaction conditions of example 3
				Evaporator I	45	275	6.5
Evaporator II	120	310	1.26

TABLE 3

Examples of the invention		V1	V2	V3	V4	V5	V6	V7	V8	V9	1	2	3
														Relative viscosity		1.294	1.259	1.322	1.287	1.318	1.292	1.277	1.283	1.287	1.276	1.269	1.291
YI (Molding 270 ℃ C.)		2.0	1.8				3.7	2.6	2.8	2.6	4.0
														YI (mold 300 ℃ C.)		2.2	1.9								4.2	4.5
YI (Molding 330 ℃ C.)		2.4	2.0				3.8	2.5	2.8	2.6	4.4
														Melt viscosity, 50s-1And 280 deg.C	P·as	1002	593	1685	1272	2075	1071	770	782	904	775	705	980
Melt viscosity, 5.000s-1And 280 deg.C	P·as	186	148	214	167	205	188	160	159	170	139	132	150
														Shear thinning ratio		5.4	4.0	7.9	7.6	10.1	5.7	4.8	4.9	5.3	5.6	5.3	6.5
A	ppm	＜5	＜5	＜5	＜5	＜5	178	＜5	53	59	639	756	657
														B	ppm	＜5	＜5	＜5	＜5	＜5	1475	226	231	256	1875	1946	1797
C	ppm	＜5	＜5	＜5	＜5	＜5	337	6	10	21	708	904	716
														D	ppm	＜5	＜5	＜5	＜5	＜5	692	138	144	175	1015	1015	801

While these new melt polymerized polycarbonates comprise multifunctional structural units, are highly branched and have pronounced non-Newtonian flow properties, they exhibit surprisingly good flow behavior. The polycarbonate of the example, using 250ppb sodium phenolate, has a high degree of branching as indicated by the shear thinning ratio. The comparative example using only 100ppb sodium phenolate had a shear-thinning ratio comparable to that of linear polycarbonate of the same viscosity. Thus, significant non-Newtonian flow properties are only achieved when a relatively large amount of branched compounds is present. The high degree of branching is achieved without the formation of compounds which, as is usually the case, have a high degree of yellowing.

Claims (11)

1. A melt polymerized polycarbonate of the general formula (1)

Wherein the square brackets in the brackets represent repeating structural units,

m is Ar or a polyfunctional compound A, and

wherein

Ar is a compound represented by the general formula (2)

Or a compound represented by the general formula (3)

Wherein

Z represents C₁～C₈Alkylidene or C₅～C₁₂Cycloalkylidene, S, SO₂Or a single bond, or a mixture of single bonds,

r is substituted or unsubstituted phenyl, methyl, propyl, ethyl, butyl, Cl or Br, and

n represents 0, 1 or 2,

wherein the polyfunctional compound A is a compound of the formula

And is present in the polycarbonate in an amount of 200 to 5000ppm,

wherein

Y is hydrogen or a compound of formula (4)

Wherein

R' is H, C₁～C₂₀Alkyl radical, C₆H₅Or C (CH)₃)₂C₆H₅The same or different, or a mixture thereof,

and

n represents 0, 1, 2 or 3,

x is Y or- (MOCOO) Y, and M and Y are as defined above.

2. The melt polymerized polycarbonate of claim 1, wherein a compound B of the formula

And wherein Ar and X are as defined in claim 1.

3. The melt polymerized polycarbonate of claim 1 or 2,

wherein a compound C of the formula

And wherein Ar and X are as defined in claim 1.

4. The melt polymerized polycarbonate of any of claims 1-2,

wherein there is present a compound D of the formula

And wherein Ar is as defined in claim 1.

5. The polycarbonate of any of claims 1-2 having a shear thinning ratio y according to the formula

y＞0.30+0.1312x^14.881，

Where x is the relative viscosity of the polycarbonate.

6. A composition comprising the melt polymerized polycarbonate of any of claims 1-5 and additional polymer components and conventional additives.

7. A molded body comprising the composition of claim 6.

8. A melt polymerization process for the preparation of the polycarbonates as claimed in claim 1, wherein diphenols and/or carbonate oligomers having terminal hydroxyl groups or terminal carbonate groups are reacted in the presence of a catalyst at a temperature of from 150 to 400 ℃ and a pressure of from 0.1MPa to 1Pa (1000mbar to 0.01mbar) to prepare the polycarbonates, and a quaternary compound of the general formula (7) is used as catalyst

Wherein

R¹、R²、R³And R⁴Represent the same or different C₁～C₁₈Alkylene radical, C₆～C₁₀Aryl or C₅～C₆Cycloalkyl, and X^-Represents an anion in which the corresponding acid-base pair H⁺+X^-- > HX has a pK of < 11_bAnd wherein amine salts, alkali metal or alkaline earth metal salts are used as cocatalysts.

9. The melt polymerization process of claim 8, wherein said co-catalyst is a hydroxide, alkoxide or phenoxide of lithium, sodium or potassium in an amount of 201 to 10,000ppb as sodium.

10. The melt polymerization process of claim 8, wherein the catalyst is a mixture of a tetraphenylphosphonium phenolate and sodium phenolate.

11. The melt polymerization process of claim 10, wherein the catalyst is a mixture of tetraphenylphosphonium phenolate and sodium phenolate, and 210 to 500ppb sodium is present.